MERCURY(II) CHLORIDE–SILVER(I) NITRITE

1

Mercury(II) Chloride–Silver(I) Nitrite

HgCl

2

AgNO

2

(HgCl

2

)

[7487-94-7]

Cl

2

Hg

(MW 271.49)

InChI = 1/2ClH.Hg/h2*1H;/q;;+2/p-2/f2Cl.Hg/h2*1h;/q2*-1;m
InChIKey = LWJROJCJINYWOX-ZZJRNXLTCY
(AgNO

2

)

[7783-99-5]

AgNO

2

(MW 153.88)

InChI = 1/Ag.HNO2/c;2-1-3/h;(H,2,3)/q+1;/p-1/fAg.NO2/qm;-1
InChIKey = KKKDGYXNGYJJRX-QGMACRPXCX

(nitromercuration

1

–

4

and

synthesis

of

nitroalkenes

from

alkenes

4

,

5

)

Form Supplied in:

white, odorless needles or powder (both

reagents).

Handling, Storage, and Precautions:

acute poison. Exposure to

all mercury compounds is to be strictly avoided. Releases toxic
Hg fumes when heated to decomposition. Protect from light.

Mixing Mercury(II) Chloride and Silver(I) Nitrite generates

Hg(NO

2

)

2

in situ, which reacts with alkenes to give nitromercu-

ration products with high regio- and stereoselectivity (eq 1).

1

–

3

The reaction with norbornene occurs without rearrangement,
indicating that carbocationic character in the transition state is
little developed. On treatment with a base (NaOH or R

3

N), the

primary adducts undergo an elimination reaction to afford
nitroalkenes (eq 1).

4

This two-step transformation represents a

general route to nitroalkenes

4

and has been employed in the

synthesis of 3-nitrocycloalkenones

5

and (E)-2-nitrovinyltri-

methylsilane.

6

However, better yields are usually obtained if

AgNO

2

/I

2

is used instead.

7

R

HgCl

2

NO

2

AgNO

2

R

HgNO

2

NO

2

NO

2

NaOH

H

2

O

O

2

N

Bu

R

NO

2

(1)

77%

80%

71%

1.

(a) Larock, R. C., Angew. Chem., Int. Ed. Engl. 1978, 17, 27. (b) Larock,
R. C., Tetrahedron 1982, 38, 1713. (c) Larock, R. C. Organomercury
Compounds in Organic Synthesis

; Springer: Berlin, 1985. (d) Larock,

R. C. Solvomercuration/Demercuration Reactions in Organic Synthesis;
Springer: Berlin, 1986.

2.

Bachman, G. B.; Whitehouse, M. L., J. Org. Chem. 1967, 32, 2303.

3.

Bloodworth, A. J.; Griffin, I. M., J. Chem. Soc., Perkin Trans. 1 1975,
695.

4.

Corey, E. J.; Estreicher, H., J. Am. Chem. Soc. 1978, 100, 6294.

5.

Vankar, Y. D.; Bawa, A., Synth. Commun. 1985, 15, 1253.

6.

Ali, S. M.; Matsuda, Y.; Tanimoto, S., Synthesis 1988, 805.

7.

Sy, W.-W.; By, A. W., Tetrahedron Lett. 1985, 26, 1193.

Pavel Ko˘covský

University of Leicester, Leicester, UK

Avoid Skin Contact with All Reagents